Lactone modified mono- or dicarboxylic acid based adduct dispersant compositions

ABSTRACT

C 5  -C 9  lactone based adduct materials are made by reacting a C 5  -C 9  lactone with a polyol to form a lactone adduct intermediate, and thereafter reacting the intermediate with an aliphatic hydrocarbyl saturated or unsaturated, straight chain or branched chain monocarboxylic or dicarboxylic acylating agent having from about one to about 165 total carbon atoms in said straight or branched chain to insure that the resulting lactone adduct is hydrocarbon soluble. The resulting adduct material are useful per se, as oil soluble dispersant additives, and are useful in fuel and lubricating oil compositions including concentrates containing the additives.

This is a division of application Ser. No. 916,108, filed 10/7/86, nowU.S. Pat. No. 4,906,399.

RELATED U.S. APPLICATIONS

This application is related to the following applications filed by theinventors herein: Ser. No. 916,218, filed Oct. 7, 1986; Ser. No.916,114, filed Oct. 6, 1989, now U.S. Pat. No. 4,866,139; Ser. No.916,113, filed Oct. 7, 1986, now U.S. Pat. No. 4,866,140; Ser. No.916,287, filed Oct. 7, 1986, now U.S. Pat. No. 4,866,135; Ser. No.916,303, filed Oct. 7, 1986, now U.S. Pat. No. 4,866,142; Ser. No.916,217, filed Oct. 7, 1986, now U.S. Pat. No. 4,866,141. All of theabove applications were filed on even date herewith. All of theserelated applications are expressly incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to oil soluble dispersant additives useful infuel and lubricating oil compositions, including concentrates containingsaid additives, and methods for their manufacture and use. Thedispersant additives are C₅ -C₉ lactone adducts, including poly (C₅ -C₉lactone) adducts which have been prepared by first reacting a C₅ -C₉lactone with a polyamine, a polyol or an amino alcohol to form anintermediate adduct, whereafter the intermediate adduct is reacted withan aliphatic hydrocarbyl monocarboxylic or dicarboxylic acylating agenthaving from about 1 to about 165, preferably from about 12 to about 165,total carbon atoms. The acylating agent can be saturated or unsaturated,branched chain or straight chain, and may contain from 1 to about 85carbon atoms in the chain. However, in preferred embodiments, theacylating agents should contain at least about tweleve carbon atoms inthe chain to insure that the resulting dispersant additives arehydrocarbon soluble.

2. Prior Art

Carboxylic acid and anhydride adducts with polyols and polyamines arewell known lubricating additives. These agents act to keep sludge andvarnish dispersed in engine oils and have been very successfulcommercially.

It is also known that polymers of 6 to 10 membered lactones such asvalerolactone or epsilon-caprolactone (hereinafter caprolactone orE-caprolactone), can be prepared by reacting the lactone monomer with ahydroxyl or amine initiator. When reacting E-caprolactone, for example,the polymerization reaction may be illustrated by the followingequations: ##STR1##

The reactions are known to be catalyzed by various esterificationcatalysts such as stannous octanoate, and a variety of differentmolecular weight products are feasible depending upon the ratio oflactone to initiator. Molecular weights on the order of form a fewhundred up to about 5000 are reproducably achievable.

Caprolactone can also be polymerized to a very high molecular weight,e.g., on the order of 100,000 or more. Typically such high molecularweight polymers do not employ initiators and preservation offunctionality is not a requirement.

It is also known to react a lactone such as E-caprolactone with a polyolto form polyesters having terminal hydroxyl groups which are useful asplasticizers.

It has now been found that improved oil soluble dispersant additives,useful in fuel and lubricating oil compositions, including concentratescontaining the additives, can be prepared by first reacting a C₅ -C₉lactone with either a polyamine, a polyol or an amino alcohol to form anintermediate adduct, and then reacting the intermediate adduct with acarboxylic acylating agent which contains at least one alkyl, alkenyl oralkynyl group having 12 or more carbon atoms to insure hydrocarbonsolubility.

There are a number of prior art disclosures relating to adducts oflactones and polyols and/or amino alcohols to polyalkenyl succinic acidor anhydride type dispersants, and to fatty acid derivative dispersants.Other prior art shows lactone polymerization reactions. In general,however, little or no prior art of direct pertinence appears to havesurfaced in regard to the present dispersants. Exemplary of the patentliterature which relates to lactone polymerization processes and/or tooil soluble dispersant additives are the following U.S. Patents: U.S.Pat. No. 4,362,635 discloses synthetic ester oils which areesterification products of monoalcohols and dicarboxylic acids or ofpolyhydric alcohols and monocarboxylic acids respectively, containing 5to 45% by weight of units of hydroxycarboxylic acids obtained fromaliphatic alcohols, aliphatic, cycloaliphatic or aromatic carboxylicacids, and lactones of aliphatic C₅ -C₁₂ hydrocarboxylic acids. Thesynthetic ester oils are suitable for the preparation of lubricants andlubricant compositions.

U.S. Pat. No. 2,890,208 discloses a process for polymerizing lactones toform lactone polyesters that are useful as plasticizers.

U.S. Pat. No. 4,062,786 and its continuation-in-part (U.S. Pat. No.4,292,184) disclose lactone oxazoline reaction products of hydrocarbonsubstituted lactone carboxylic acids such as polybutyl lactonecarboxylic acid, with a 2,2-disubstituted-2-amino-1-alkanol such astris-(hydroxymethyl) amino-methane (THAM). The reaction products andtheir derivatives are disclosed as being useful additives in oleaginouscompositions such as sludge dispersants for lubricating oil.

U.S. Pat. No. 4,379,914 and its continuation-in-part (U.S. Pat. No.4,463,168) disclose the preparation of polycaprolactone polymers byreacting E-caprolactone with a diamine wherein one of the amine groupsof the diamine is a tertiary amine and the other is a primary orsecondary amine. The polycaprolactone polymers are disclosed as beinguseful for neutralizing certain sulfonic acid-containing polymers toform amine-neutralized, sulfonated derivatives which can be combinedwith an alkyl benzene sulfonic acid to give a surfactant which containsester groups, hydroxyl groups and amine-neutralized sulfonate groups.

U.S. Pat. No. 3,169,945 discloses the preparation of lactone polyesterswhich are useful as plasticizers and as intermediates for preparingelastomers and foams. The polyesters can be prepared by reacting alactone such a E-caprolactone with an initiator such as an alcohol,amine or amino alcohol. A similar disclosure is contained in U.S. Pat.No. 3,284,417.

U.S. Pat. No. 3,025,323 relates to a class of diols which are derivedthrough the action of omega-lactones on the primary amine groups ofmonoalkanolamines and on the amine groups of primary diamines. Thecompounds disclosed in this patent are useful as intermediates in thesynthesis of polymers and as softeners and sizes for paper, leather andother porous materials.

U.S. Pat. No. 3,436,463 discloses N-substituted-gamma hydroxycarboxylicacid amides which are useful as nematocides and insecticides. Thecompounds of this patent are prepared by reacting an organic primaryamine with a lactone such as gamma-butyrolactone or gamma-valerolactone.

U.S. Pat. No. 4,532,058 discloses as a motor oil dispersant, aspirodilactone condensation product formed by heating alkenyl succinicanhydrides in the presence of a basic catalyst, and then heating theresulting bicyclic spirodilactone condensation product with a polyamineor polyamine alcohol. It should be emphasized that this patent describesthe intermolecular decarboxylation of an alkenyl succinic anhydride atelevated temperatures to form a condensation product and carbon dioxideas a by-product. This prior art is not concerned with polymerizablelactones which are the subject of the instant invention.

U.S. Pat. No. 2,638,449 discloses lubricating oil additives derived fromalkenyl succinic anhydride esters of hydroxy compounds containing fattyacid amide groups.

U.S. Pat. No. 4,540,809 discloses acrylate esters of dipentaerythritolcaprolactone condensates. The esters are useful as vehicles for paintsand can be hardened by ionizing radiation or thermal means.

U.S. Pat. No. 4,086,294 discloses water soluble polycaprolactone-epoxideadducts which are produced by reacting a polycaprolactone polyol, adiepoxide and an anhydride of a polycarboxylic acid, such as substitutedor unsubstituted succinic anhydride. The polycaprolactone-epoxideadducts are useful in the preparation of aqueous coating compositions.Similar polycaprolactone-epoxide adducts are disclosed in U.S. Pat. No.4,261,871.

U.S. Pat. No. 3,438,943 relates to polyesters which are derived fromoxazoline polyols which are prepared by reacting an acid or acidderivative and a polyhydroxy amine such as THAM. In cases where the acidis a fatty acid, the oxazolines are used as lubricants. Condensation ofthe oxazoline alcohols and polycarboxylic acids, including fat derivedacids, e.g., azealic, yield polyesters that are used in aqueous paints.

U.S. Pat. No. 4,397,750 teaches the preparation of hydroxy substitutedpyrrolidone esters from butyrolactones and polyhydroxyamines.Corresponding hydroxyamide side-products are also disclosed. Thedisclosed esters are useful as additives for lubricants and fuels.

U.S. Pat. No. 4,247,671 discloses the preparation of oxazoline alcoholsvia the condensation of, for example, caprolactone with an appropriateamine, for example, 2-amino-2-methyl-1-propanol. The oxazoline alcoholscan be used to prepare oxazoline-containing polymer coatings. Analogousadducts prepared from butyrolactone and monohydroxy amino alcohols aredisclosed in U.S. Pat. No. 4,448,905.

U.S. Pat. No. 3,493,568 discloses diol amides prepared from caprolactoneand a monohydroxy amino alcohol. The diol amides can be cyclodehydratedto form oxazolines and oxazines which can be polymerized to yieldcrosslinked polymeric structures.

U.S. Pat. No. 4,017,406 discloses ester derivatives of long chaindicarboxylic anhydrides such as octadecenyl and polyisobutenylsuccinicanhydrides and aldehyde/THAM adducts for use as additives for oleaginouscompositions.

U.S. Pat. No. 3,062,631 discloses condensation products of abeta-lactone and a polyamine which are useful as oil additives.

U.S. Pat. No. 2,290,154 discloses the use of amides of polyamines suchas tetraethylene pentamine as a demulsifier. The acylating agents whichare used to prepare the amides of this patent include straight andbranched chain, saturated and unsaturated fatty acids or derivativesthereof.

U.S. Pat. No. 3,424,771 discloses the reaction products of fatty acidacylated polyamines and butyrolactones for use as aids in detergentcompositions.

U.S. Pat. No. 2,409,275 relates to lubricating oil additives derivedfrom the reaction of an anhydride of an acetic acid ester of a hydroxypolycarboxylic acid, e.g., citric acid with a carboxylic acid, e.g.,fatty acid partial amide of an alkylene polyamine.

U.S. Pat. No. 3,341,458 relates to a lime soap detergent derived from2-p-dioxanone and acylated ethanol amines.

U.S. Pat. No. 3,894,849 discloses a motor fuel additive which is anacrylated polyalkylene polyamine.

U.S. Pat. No. 2,759,894 discloses ester-oxazolines of fatty acids whichare useful as lubricating oil additives.

U.S. Pat. No. 3,483,145 discloses polyester monooxazolines used as amonomer in the preparation of polymers.

U.S. Pat. No. 4,263,014 discloses fuel compositions containing dimeracids admixed with lactoneimidazoline derivatives.

U.S. Pat. No. 4,415,728 discloses the preparation of caprolactonecopolyester diols via copolymerization of caprolactone and analkoxylated Empol dimer acid. The diols of this patent are used in thepreparation of polyurethane binders.

U.S. Pat. No. 4,292,187 relates to a condensation products which areprepared from at least one aliphatic or cycloaliphatic polyol, at leastone aliphatic saturated or unsaturated C₆ -C₂₂ hydroxycarboxylic acid orlactone thereof, and at least one saturated or unsaturated C₆ -C₂₄monocarboxylic acid. The condensation products of this patent are usefulas effective lubricants for the working of metals or for admixture withother lubricating oils and conventional additives.

U.S. Pat. No. 4,234,435 discloses as oil additives, polyalkylenesubstituted dicarboxylic acids derived from poly-alkylenes having aM_(n) of 1300 to 5,000 and containing at least 1.3 dicarboxylic acidgroups per polyalkylene. In Example 34 of this patent, apolyisobutene-substituted succinic acylating agent is reacted withcaprolactam in the presence of mineral oil and sodium hydroxide.

U.S. Pat. No. 3,381,022 relates to ester derivatives of substantiallysaturated polymerized olefin-substituted succinic acid wherein thepolymerized olefin substituent contains at least about 50 aliphaticcarbon atoms and host a molecular weight of about 700 to 5,000. Theesters include the acidic esters, diesters, and metal salt esterswherein the ester moiety is derived from monohydric and polyhydricalcohols, phenols and naphthols. The ester derivatives are useful asadditives in lubricating compositions, fuels, hydrocarbon oils and powertransmission fluids. A related application, i.e., U.S. Pat. No.3,522,179, relates to lubricating comppositions comprising a majoramount of a lubricating oil and a minor proportion of an esterderivative of a hydrocarbon-substituted succinic acid sufficient toimprove the detergency of the lubricating composition. The esterderivatives are similar to those described in U.S. Pat. No. 3,381,022and contain at least about 50 aliphatic carbon atoms. The hydrocarbonsubstituent may be derived from a polymerized lower monoolefin having amolecular weight of from about 700 to about 5000.

All of the above discussed patents are expressly incorporated herein byreference in their entirety.

Additional exemplary prior art disclosures, which are expresslyincorporated herein by reference in their entirety are U.S. Pat. Nos.2,290,154; 2,568,619; 2,767,144; 3,062,631; 3,087,936; 3,131,150;3,154,560; 3,172,892; 3,198,736; 3,202,678; 3,215,707; 3,219,666;3,231,587; 3,325,484; 3,269,946; 3,272,743; 3,272,746; 3,278,550;3,284,409; 3,284,417; 3,288,714; 3,361,673; 3,367,895; 3,379,693;3,390,086; 3,401,118; 3,403,102; 3,455,827; 3,562,159; 3,576,743;3,632,510; 3,699,165; 3,684,771; 3,708,522; 3,792,061; 3,799,877;3,836,470; 3,836,471; 3,838,050; 3,838,052; 3,879,308; 3,912,764;3,927,041; 4,062,786; 4,102,798; 4,110,349; 4,113,639; 4,116,875;4,116,876; 4,123,373; 4,151,173; 4,167,073; 4,169,836; 4,263,153;4,292,184; 4,379,914; 4,463,168; 4,486,326; 4,502,970; 4,517,104;4,532,058; 4,536,547 and U.S. Pat. No. Re. 26,330.

SUMMARY OF THE INVENTION

Despite the efficacy of prior art dispersant and oleaginouscompositions, there is a need for more efficient and less costlydispersants which can either perform better, or perform well at lowerdispersant levels. Accordingly, it is a principal object of thisinvention to provide novel lactone adduct based dispersants which areeffective, and readily prepared under typical dispersant manufacturingconditions.

Another object is to provide a novel class of poly (C₅ -C₉ lactone)adduct dispersants.

Another object is to provide a process for preparing efficientdispersants by reacting a saturated or unsaturated, straight or branchedchain natural or synthetic, aliphatic hydrocarbon monocarboxylic ordicarboxylic acylating agent having from about 1 to about 165, andpreferably from about 12 to about 165, total carbon atoms and from about1 to about 85, and preferably from about 12 to about 85, carbon atoms inthe straight or branched chain with a lactone adduct formed by reactinga C₅ -C₉ lactone with a polyamine, a polyol, an amino alcohol or amixture thereof.

A further object is to provide lubricant compositions and concentratescontaining the novel C₅ -C₉ lactone based dispersants of this invention.

Yet another object is to provide a novel class of preferable oil solubledispersants from fatty acid acylating agents which have at least one C₁₂or higher straight or branched chain alkyl, alkenyl or alkynyl group intheir structure and which are reactive with an intermediate adductformed by reacting a C₅ -C₉ lactone with a polyamine, a polyol, an aminoalcohol, or a mixture thereof.

Still another object is to provide C₅ -C₉ lactone-polyol adducts whichhave been post-reacted with a long chain fatty acid or dimer thereof, aswell as lubricant compositions and concentrates containing thepost-reacted adducts.

Another object is to provide C₅ -C₉ lactone-polyamine adducts which havebeen post-reacted with a long chain fatty acid or dimer thereof, as wellas lubricant compositions and concentrates containing the post-reactedadducts.

Still another object is to provide C₅ -C₉ lactone-amino alcohol adductswhich have been post-reacted with, a long chain fatty acid or dimerthereof, as well as lubricant compositions and concentrates containingthe post-reacted adducts.

Still another object is to provide metal complexes and post-treatedderivatives, e.g., borated derivatives, of the C₅ -C₉ lactone deriveddispersants of this invention, as well as lubricant compositions andconcentrates containing such post-treated derivatives.

The manner in which these and other objects can be achieved will beapparent from the detailed description of the invention which appearshereinbelow.

In one aspect of this invention, one or more of the above objects can beachieved by reacting a C₅ -C₉ lactone with a polyamine to yield ahydroxyl terminated amide structure containing a sequence of methyleneunits between the hydroxyl and amide groups, and thereafter reacting thehydroxyl terminated amide structure with a saturated or unsaturated,straight or branched chain natural or synthetic, aliphatic hydrocarbonmonocarboxlic or dicarboxylic acylating agent having from about 1 toabout 165 total carbon atoms and from about 1 to about 85 carbon atomsin the straight or branched chain.

In another aspect, one or more of the objects of this invention can beachieved by heating a C₅ -C₉ lactone such as E-caprolactone at atemperature of at least about 30° C., and preferably from about 75° C.to about 180° C. with a polyamine, and then heating the resulting adductwith a saturated or unsaturated, straight or branched chain natural orsynthetic, aliphatic hydrocarbon monocarboxlic or dicarboxylic acylatingagent having from about 12 to about 165 total carbon atoms and fromabout 12 to about 85 carbon atoms in the straight or branched chain.And, in a further aspect, one or more objects of this invention areachieved by providing acylated C₅ -C₉ lactone adducts produced by such aprocess.

One or more objects of this invention can be illustrated in connectionwith the reaction between a C₅ -C₉ lactone such as E-caprolactone and apolyamine such as tetraethylene pentamine (TEPA) to form a hydroxylterminated amide structure containing a sequence of five methylene unitsbetween the hydroxyl unit and the amide, followed by the reactionbetween the hydroxyl terminated amide structure and a C₁₂ + alkylcarboxylic acid material or a C₁₂ -C₁₈ fatty acid or dimer thereof toform a hydrocarbon soluble dispersant. This process can be characterizedby the following Examples equations: ##STR2##

Still other objects can be illustrated in connection with the reactionbetween E-caprolactone and a polyol such as pentaerythritol to form apolyol ester intermediate, which intermediate is then reacted with along chain fatty acid or dimer thereof to form a fattyacid-polyol-caprolactone dispersant. This process can be characterizedby the following general equations: ##STR3##

Still other objects can be illustrated in connection with the reactionbetween E-caprolactone and an amino alcohol such as2-amino-2-(hydroxymethyl)-1,3-propanediol (THAM) to form a polyol amidewhich, upon heating, forms a hydroxy-oxazoline intermediate. Either thepolyol amide or the hydroxy-oxazoline intermediate can then be reactedwith a long chain fatty acid or dimer thereof to form a hydrocarbonsoluble dispersant. This process can be characterized by the followinggeneral equations: ##STR4##

The novel products of this invention are useful per se as an additive,e.g., a dispersant additive, for example, in the same manner asdisclosed in U.S. Pat. No. 3,219,666 where prior art derivatives ofpolyalkenyl succinic acids and nitrogen compounds are used asdispersant/detergents in lubricants, especially lubricants intended foruse in the crankcase of internal combustion engines, gears, and powertransmitting units. Accordingly, one or more objects of this inventionare achieved by providing lubricating oil compositions, e.g., automatictransmission fluids, heavy duty oils suitable for use in the crankcasesof gasoline and diesel engines, etc. containing the novel C₅ -C₉ lactonebased products of this invention. Such lubricating oil compositions maycontain additional additives such as viscosity index improvers,antioxidants, corrosion inhibitors, detergents, pour depressants,antiwear agents, etc.

Still further objects are achieved by providing concentrate compositionscomprising from about 20 to about 80 weight % of a normally liquid,substantially inert, organic solvent/diluent, e.g., mineral lubricatingoil, or other suitable solvent/diluent and from about 20 to about 80weight % of a C₅ -C₉ lactone based dispersant, as mentioned above anddescribed in more detail hereinafter.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Lactone Material

Useful lactone compounds for forming the intermediates or lactoneadducts by reaction with a polyamine, polyol, or amino alcohol includelactones having at least five carbon atoms in the lactone ring, e.g., C₅-C₉ lactones. The lactone may be substituted or unsubstituted and thesubstituents, if any, may comprise, for example, alkyl, aryl, aralkyl,cycloalkyl, alkoxy or other which would not interfere with the ringopening reaction and adduct formation. The preferred lactones have nomore than two substituent groups, and the more preferred lactones areunsubstituted.

Non-limited examples of the useful lactones include delta-valerolactone,methyl-delta-valero-lactone, E-caprolactone, methyl-E-caprolactone,dimethyl-E-caprolactone, methoxy-E-caprolactone,cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone, caprylolactone,methyl-caprylolactone, and the like, with E-caprolactone beingparticularly preferred.

Reaction of the Lactone with a Polyamine

The above lactones such as E-caprolactone are cyclic esters which can bereacted with a polyamine to yield hydroxyl terminated amide adductstructure containing a sequence of methylene units between the hydroxyand the amide. In the case of E-caprolactone, which is a preferredlactone for use in this invention, the adduct contains a sequence offive methylene units between the hydroxyl and the amide groups. Thestoichiometry of the lactone and polyamine determines the length of thepolyester sequence in the resulting adducts as can be appreciated fromEquation 3 above. Once these lactone-polyamine adducts are formed,reaction with an acylating agent such as an alkyl carboxylic acidmaterial, e.g. octadecenyl succinic anhydride or a long chain fattyacid, e.g., isostearic acid, linoleic acid, oleic acid or dimers therof,can be effected through the hydroxyl groups thereby forming an esterlink with the acylating agent. The resulting materials, which areillustrated generally in Equation 4, display excellent bench test.

The chemistry of the lactone-polyamine reaction is such that primaryamino functionality is more reactive than the secondary aminofunctionality in the polyamine structure and therefore the amidestructure illustrated in Equation 3 will be the favored product. It isalso possible, however, that the secondary amino functionality or thehydroxyl functionality of the resulting adducts can react withadditional lactone molecules to form a diversity of structures.

In the reactions discussed above, the average degree of polymerization(DP) of the lactone monomer i.e., the sequence of lactone units in a rowin the lactone adduct, may vary depending upon the intended application.At DP's of much greater than about 10 the dispersants formed from thelactone adducts can exhibit crystallinity; a characteristic which isundesirable in an oil soluble dispersant due to the consequent highviscosity, or even solid, oil products which can be obtained. However,at lower DP's, oil soluble adducts posessing low viscosity and desirablesludge and varnish inhibition characteristics are obtained. Accordingly,regardless of the identity of the lactone adduct, the degree ofpolymerization (DP) should be between about 0.2 and about 100, morepreferably between about 0.2 and about 50, and most preferably between0.5 and about 20. For optimal dispersant performance sequences of fromabout 1 to about 5 lactone units in a row are preferred. The degree ofpolymerization can be controlled by controlling the reaction conditions,including the mole ratio of lactone to amine compound, amount ofcatalyst employed, and the like.

Useful amine compounds for reaction with the lactone material includepolyamines of about 2 to 60, e.g. 3 to 20, most preferably 3 to 10,total carbon atoms in the molecule. These amines may be hydrocarbylamines or may be hydrocarbyl amines including other noninterferinggroups, e.g., alkoxy groups, amide groups, nitrile groups, imidazolinegroups, and the like. Preferred amines are aliphatic saturated amines,including those of the general formula: ##STR5## wherein R and R' areindependently selected from the group consisting of hydrogen, C₁ to C₂₅straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals,each s is the same or a different number of from 2 to 6; preferably 2 to4; and t is a number of from 0 to 10, preferable 2 to 7. If t=0, then atleast one of R or R' must be H such that there are at least two ofeither primary or secondary amino groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane: 1,3-diaminopropane: 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2propylene) triamine;di-(1,3-propylene) triamine; N,N-dimethyl-1-1,3-diamino-propane;N,N-di-(2-aminoethyl) ethylene diamine; N-dodecyl-1-1,3-propane diamine;di-, and tri-tallow amines; amino morpholines such as N-(3-aminopropylmorpholine; etc.

Other useful amine compounds include: alicylic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, morpholines, and N-aminolakyl piperazines of thegeneral formula: ##STR6## wherein G is independently selected from thegroup consisting hydrogen and omega-(non-tertiary)aminoalkylene radicalsof from 1 to 3 carbon atoms, and p is a number of from 1 to 4.Non-limiting examples of such amines include 2-pentadecyl imidazoline,N-(2-aminoethyl) piperazine, etc.

Commercial mixtures of amine compounds advantageously may be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. A low cost mixture ofpoly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms permolecule are available commercially under trade names as "Polyamine H","Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxalkylene polyamines such as those ofthe formulas:

    NH.sub.2 -alkylene--O-alkylene).sub.m NH.sub.2             III

where m has a value of about 3 to 70 and preferably 10 to 35: and

    R[alkylene(O-alkylene).sub.n NH.sub.2 ].sub.a              IV

where n has a value of about 1 to 40 with the provision that the sum ofall the n's is from about 3 to about 70 and preferably from about 6 toabout 35. R is a substituted saturated hydrocarbon radical of up to 10carbon atoms, wherein the number of substituents on the R group isrepresented by the value of "a", which is a number from 3 to 6. Thealkylene groups in either formula III or IV may be straight or branchedchain containing about 2 to 7, and preferably about 2 to 4 carbon atoms.

The above polyoxyalkylene polyamines, preferably polyoxyalkylenediamines and polyoxyalkylene triamines, may have average molecularweights ranging from about 200 to about 4,000 and preferably from about400 to about 2,000. The preferred polyoxyalkylene polyamines include thepolyoxyethylene and polyoxypropylene diamines and the polyoxypropylenetriamines having average molecular weight ranging from about 200 to2,000. The polyoxyalkylene polyamines are commercially available and mybe obtained, for example, from the Jefferson Chemical Company, Inc.under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403",etc.

The polyamine is readily reacted with the lactone, with or without acatalyst, simply by heating a mixture of the lactone and polyamine in areaction vessel in the absence of a solvent at a temperature of about30° C. to about 200° C., more preferably to a temperature of about 75°C. to about 180° C., and most preferably at about 90° C. to about 160°C., for a sufficient period of time to effect reaction. Optionally, asolvent for the lactone, polyamine and/or adduct can be employed tocontrol viscosity and/or reaction rates.

In one preferred embodiment of the invention, the C₅ -C₉ lactone such asE-caprolactone is reacted with a polyamine such as tetraethylenepentamine in a 2:1 molar ratio in accordance with the Equation above.However, in accordance with the reaction scheme illustrated in Equation3 above, it will be appreciated that the mole ratio of lactone topolyamine can be varied widely as a means for controlling the length ofthe sequence of lactone units in the adduct. In this latter regard, themole ratio of lactone to polyamine may vary from about 10:1 to about0.1:1, more preferably from about 4:1 to about 0.2:1, and mostpreferably from about 2:1 to about 0.4:1.

It also will be appreciated that the half ester may be formed, and thatin most cases, the reaction product will comprise a mixture of the halfester and diester.

Catalysts useful in the promotion of the above-identifiedlactone-polyamine reactions are selected from the group consisting ofstannous octanoate, stannous hexanoate, stannous oxalate, tetrabutyltitanate, a variety of metal organic based catalyst acid catalysts andamine catalysts, as described on page 266, and forward in a book chapterauthorized by R. D. Lundberg and E. F. Cox entitled, "Kinetics andMechanisms of Polymerization: Ring Opening Polymerization", edited byFrisch and Reegen, published by Marcel Dekker in 1969, wherein stannousoctanoate is an especially preferred catalyst. The catalyst is added tothe reaction mixture at a concentration level of about 50 to about10,000 parts per weight of catalyst per one million parts of the totalreaction mixture.

Reaction of the Lactone with a Polyol

In another aspect of the invention, the lactone adduct dispersantprecursors are prepared by reacting the above discussed C₅ -C₉ lactoneswith a polyol instead of with a polyamine.

Suitable polyol compounds which can be used in this esterificationreaction include aliphatic polyhydric alcohols containing up to about100 carbon atoms and about 2 to about 10 hydroxyl groups. These alcoholscan be quite diverse in structure and chemical composition, for example,they can be substituted or unsubstituted, hindered or unhindered,branched chain or straight chain, etc. as desired. Typical alcohols arealkylene glycols such as ethylene glycol, propylene glycol, trimethyleneglycol, butylene glycol, and polyglycol such as diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol,tripropylene glycol, dibutylene glycol, tributylene glycol, and otheralkylene glycols and polyalkylene glycols in which the alkylene radicalcontains from two to about eight carbon atoms. Other useful polyhydricalcohols include glycerol, monomethyl ether of glycerol,penthaerythritol, dipentaerythritol, tripentaerythritol,9,10-dihydroxystearic acid, the ethyl ester of 9,10-dihydroxystearicacid, 3-chloro-1,2-propanediol, 1,2-butanediol, 1,4-butanediol,2,3-hexanediol, 2,3-hexanediol, pinacol, tetrahydroxy pentane,erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol,1,4-cyclohexanediol, 1,4-(2-hydroxyethyl)-cyclohexane,1,4-dihydroxy-2-nitrobutane, 1,4-di-(2-hydroxyethyl)-benzene, thecarbohydrates such as glucose, rhamnose, mannose, glyceraldehyde, andgalactose, and the like, amino alcohols such asdi-(2-hydroxyethyl)amine, tri-(3-hydroxypropyl)amine,N,N'-di-(hydroxyethyl)ethylenediamine, copolymer of allyl alcohol andstyrene, N,N-di-(2-hydroxylethyl) glycine and esters thereof with lowermono-and polyhydric aliphatic alcohols etc.

Included within the group of aliphatic alcohols are those alkane polyolswhich contain ether groups such as polyethylene oxide repeating units,as well as those polyhydric alcohols containing at least three hydroxylgroups, at least one of which has been esterified with a mono-carboxylicacid having from eight to about 30 carbon atoms such as octanoic acid,oleic acid, stearic acid, linoleic acid, dodecanoic acid, or tall oilacid, Examples of such partially esterified polyhydric alcohols are themono-oleate of sorbitol, the mono-oleate of glycerol, the mono-stearateof glycerol, the di-stearate of sorbitol, and the di-dodecanoate oferythritol.

A preferred class of ester intermediates are those prepared fromaliphatic alcohols containing up to 20 carbon atoms, and especiallythose containing three to 15 carbon atoms. This class of alcoholsincludes glycerol, erythritol, pentaerythritol, dipentaerythritol,tripentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose,1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanetriol, 1,2,4-hexanetriol,1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol,1,2,4-butanetriol, quinic acid,2,2,6,6-tetrakis(hydroxymethyl)-cyclohexanol, 1,10-decanediol,digitalose, and the like. The esters prepared from aliphatic alcoholscontaining at least three hydroxyl groups and up to fifteen carbon atomsare particularly preferred.

An especially preferred class of polyhydric alcohols for preparing thelactone adducts used as starting materials in the present invention arethe polyhydric alkanols containing three to 15, especially three to sixcarbon atoms and having at least three hydroxyl groups. Such alcoholsare exemplified in the above specifically identified alcohols and arerepresented by glycerol, erythritol, pentaerythritol, mannitol,sorbitol, 1,2,4-hexanetriol, and tetrahydroxy pentane and the like.

The polyol is readily reacted with C₅ -C₉ lactone e.g., E-caprolactone,by heating a mixture of the polyol and lactone in a reaction vessel inthe absence of a solvent at a temperature of about 50° C. to about 200°C., more preferably to a temperature of about 75° C. to about 180° C.,and most preferable at about 90° C. to about 160° C., for a sufficientperiod of time to effect reaction. Optionally, a solvent for thelactone, polyol and/or the resulting adduct may be employed to controlviscosity and/or the reaction rates.

In one preferred embodiment of the invention, the C₅ -C₉ lactone, e.g.,E-caprolactone is reacted with a polyol, e.g., pentaerythritol inaccordance with the reaction scheme illustrated in Equation 5 wherein a1:1 mole ratio of caprolactone to pentaerythritol is shown. In practice,the ratio of lactone to polyol may vary considerable as a means ofcontrolling the length of the sequence of the lactone units in theadduct. For example, the mole ratio of lactone to polyol may vary fromabout 10:1 to about 0.1:1, more preferably from about 5:1 to about0.2:1, and most preferably from about 2:1, to about 0.4:1. As is thecase with the lactone/polyamine adducts, it is preferable to maintainthe average degree of polymerization of the lactone monomer below about100, with a degree of polymerization on the order of from about 0.2 toabout 50 being preferred, and from about 0.2 to about 20 being morepreferred. For optimum dispersant performance, sequences of from about 1to about 5 lactone units in a row are preferred.

Catalysts useful in the promotion of the lactone-polyol reactions arethe same as those which are useful in connection with thelactone-polyamine reactions discussed above. The catalyst may be addedto the reaction mixture at a concentration level of from about 50 toabout 10,000 parts of catalyst by weight per one million parts by weightof the total reaction mixture.

Reaction of the Lactone with an Amino Alcohol

In a manner analogous to that described for the lactone-polyaminereaction and for the lactone-polyol reaction, the C₅ -C₉ lactone can bereacted with an amino alcohol to form an adduct or intermediate whichcan be further reacted with an acylating agent to form the dispersantsof this invention.

Suitable amino alcohol compounds which can be reacted with the lactoneinclude those containing up to about 50 total carbon atoms andpreferably up to about 10 total carbon atoms, from 1 to about 5 nitrogenatoms, preferably from 1 to 3 nitrogen atoms, and from 1 to about 15hydroxyl groups, preferably from about 1 to 5 hydroxyl groups. Preferredamino alcohols include the 2,2-disubstituted-2-amino-1-alkanols havingfrom two to three hydroxy groups and containing a total of 4 to 8 carbonatoms. These amino alcohols can be represented by the formula: ##STR7##wherein X is an alkyl or hydroxyalkyl group with the alkyl groups havingfrom 1 to 3 carbon atoms wherein at least one, and preferably both, ofthe X substituents is a hydroxyalkyl group of the structure --(CH₂)_(n)OH, n being 1 to 3. Examples of such amino alcohols include:2-amino-2-methyl-1,3 propanediol; 2-amino-2-ethyl-1,3-propanediol; and2-amino-2-(hydroxymethyl)1,3-propanediol; the latter also being known asTHAM or tris (hydroxymethyl) amino methane. THAM is particularlypreferred because of its effectiveness, availability and low cost.

The amino alcohol is readily reacted with the C₅ -C₉ lactone by heatinga mixture of the lactone and amino alcohol in a reaction vessel in theabsence of a solvent at a temperature of about 50° C. to about 200° C.,more preferably at temperature of about 75° C. to about 180° C., andmost preferably at about 90° C. to about 160° C., for a sufficientperiod of time to effect reaction. Optionally, a solvent for thelactone, amino alcohol and/or the reaction product may be used tocontrol viscosity and/or the reaction rates.

In one preferred embodiment of the invention, the C₅ -C₉ lactone, e.g.,E-caprolactone is reacted with an amino alcohol, e.g., THAM inaccordance with the reaction scheme illustrated in Equation 7. As shownin Equation 7, one mole of E-caprolactone is reacted with one mole ofTHAM to form a polyhydroxy terminated amide which, upon further heating,rearranges to form a hydroxy-oxazoline.

It will be appreciated that the mole ratio of lactone to amino alcoholmay be varied considerably and further that the reaction product, inmost cases, will comprise a mixture of adducts. In this latter regard,it is contemplated that the mole ratio of lactone to amino alcohol mayvary from about 10:1 to about 0.1:1, more preferably from about 5:1 toabout 0.5:1, and most preferably from about 2:1 to about 0.6:1. It alsocontemplated that the average degree of polymerization of the lactone inthe lactone/amino alcohol adduct preferably will be less than about 100.Preferably, the degree of polymerization is from about 0.2 to about 50,and more preferably from about 0.2 to about 20. For optimum dispersantperformance, sequences of from about 1 to about 5 lactone units in a roware preferred.

Catalysts useful in the promotion of the lactone-amino alcohol reactionsare the same as those which are useful in connection with thelactone-polyamine and lactone-polyol reactions, and correspondingamounts of catalyst may be employed.

The Acylating Agents

The acylating agents which may be reacted with the lactone-polyamine,lactone-polyol and/or lactone-amino alcohol adducts to form thedispersant additives of the invention are saturated and unsaturated,straight chain or branched chain, natural or synthetic, aliphatichydrocarbon monocarboxylic or dicarboxylic acylating agents, e.g., acid,anhydride or ester materials, which have from about 1 to about 165 totalcarbon atoms, and preferably from about 12 to about 165 carbon atoms,and from about 1 to about 85 carbon atoms in the straight or branchedchain. Preferably, there are from about 12 to about 85 carbon atoms inthe straight or branched chain to insure hydrocarbon solubility of theacylated products.

In one preferred aspect, the acylating agent comprises an acid of theformula

    RCOOH                                                      VI

where R is C₁ -C₁₆₄ saturated or unsaturated, straigt or branchedaliphatic hydrocarbyl. Included are alkanoic, alkenoic and alkadienoicacids. Carboxylic acids wherein the hydrocarbyl portion of the moleculeis of a straight chain configuration are preferred since, generally,less severe reaction conditions are required for acylation with suchacid. Representative carboxylic acids include dodecanoic, dodecenoic,tridecanoic, tridecenoic, tetradecanoic, tetradecenoic, hexadecanoic,hexadecenoic, octodecanoic, octadecenoic, octadecadienoic, eicosanoic,uneicosanoic and doeicosanoic acids. Mixed acids can be employed, themixture being preferred because of generally lower cost and betterproperties of fluidity and greater solubility. Acid mixtures such asthose obtained by hydrolysis of natural fats and oils are useful.Included are those derived from coconut oil, corn oil, cottonseed oil,tallow and soybean oil. The acids prepared from tallow are ordinarilymixtures of tetradecanoic, tetradecenoic, hexadecanoic, hexadecenoic,octadecanoic, octadecenoic, octadecadienoic and eicosandoic acids; thoseprepared from soybean oil are mixtures containing hexadecanoic,octadecanoic, octadecadienoic and eicosanoic acids; those prepared fromcotton seed oil are mixtures ordinarily containing tetradecanoic,hexadecanoic, octadecanoic, octadecadienoic and eicosanoic acids; andthose prepared from cocanut oil contain decanoic, dodecanoic,tetradecanoic, hexadecanoic, octadecanoic, octadecenoic andoctadecatrienoic acids with a very small amount of octanoic acid. Aparticularly useful and preferred acid mixture is tall oil fatty acidobtained from tall oil. Tall oil is a mixture of rosin and fatty acidsreleased by acidulation of the black liquor soap skimmed off the blackliquor from the sulfite process in the manufacture of Kraft paper. Crudetall oil is commonly fractionally distilled to provide various cutswherein the ratio of fatty acids to rosin acids varies from 1:99 to99:1. In the context of this description tall oil fatty acid is intendedto include tall oil compositions having a fatty acid content of at leastabout 50% by weight, the balance being mainly rosin acids in admixturewith minor amount of unsaponifiable materials of unknown chemicalcomposition. The fatty acids in tall oil fatty acids consist mainly ofoleic, linoleic, conjugated linoleic, palmitic, stearic, palmitoleic,arachidic and behenic acids. Tall oil fatty acids which are commericallyavailable include those with the following compositions: palmitic(0.1-5.3%), palmitoleic (0.1-2.1%); stearic (2.1-2.6%); oleic(39.3-49.5%); linoleic (38.1-41.4%); eicosanoic (1.2- 1.9%);eicosadienoic (0.5-3.2%); eicosatrienoic (0.4-2.9%); and behenic(0.4-0.9%) acids, with the balance being rosin acids, unidentified acidsand unaponifiable materials.

In another preferred aspect, the acylating agent may comprise the dimerof a C₁₂ -C₁₈ fatty acid. Specific fatty acid dimers which can beemployed include the dimers of, for example, stearic acid, isostearicacid, linoleic acid, linolenic acid, oleic acid, 9, 11-octadecadienoicacid and eleostearic acid. Effective dimer acids can be prepared fromnaturally occurring materials, such as linseed fatty acids, soya beanfatty acids and other natural unsaturated fatty acids. A preparation ofdimer acids is disclosed in U.S. Pat. No. 2,632,659. Suitable dimeracids are available commercially, for example, under the name Empol 1022(a dimer of linoleic acid) and Empol 1010 (a dimer of acid). Both Empol1022 and Empol 1010 are well known as rust inhibitors for motor fuelcompositions.

Other suitable acylating agents include dicarboxylic acid materials,e.g., acid anhydride, or ester materials, which are substituted with aC₁₂ -C₁₈ hydrocarbyl group, generally an alkenyl group, and whichcontain from about 0.7 to about 2.0, preferably 1.00 to 1.5 moles permole of hydrocarbyl of an alpha or beta unsaturated C₄ -C₁₀ dicarboxylicacid or anhydride or ester thereof, such as fumaric acid, itaconic acid,maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate,chloromaleic anhydride, etc.

Preferred hydrocarbyl substituents are alkyl, alkenyl and alkynyl groupscontaining from about twelve to about eighteen carbon atoms. Hydrocarbylsubstituents of a straight chain configuration are preferred since theygenerally permit the use of less sever acylation conditions. Octadecenylsuccinic anhydride is an example of a suitable hydrocarbyl substituteddicarboxylic acid material for use as the acylating agent in accordancewith the present invention.

Reaction of the Acylating Agent with the Lactone Adduct

In order to form the lactone based dispersants of the present invention,the acylating agent must be reacted with a lactone-polyamine adduct, alactone-polyol adduct, a lactone-amino alcohol adduct or a mixturethereof.

All of the above lactone adducts are readily reacted with the acylatingagent, e.g., isostearic acid, by heating a mixture of the lactone adductand the acylating agent, with or without an oil diluent, to about 100°to 250° C., preferably 160° to 210° C., generally for 1 to 10, e.g., 2to 6 hours, until the desired amount of water is removed. Reactionratios can vary considerable, depending upon the reactants, amount ofexcess lactone adduct, type of bonds formed, etc. generally from 0.1 to4.0 preferably 0.5 to 3.0 e.g., 0.5 to 1.0 moles of lactone adduct,e.g., E-caprolactone/pentaerythritol, are used per mole of the acylatingagent moiety content. Variations beyond these ratios can be practiced,but normally such variations would not be desirable.

The reaction between the lactone-polyamine adduct and the acylatingagent acid material may be exemplified by the following reaction schemewhich which represents the esterification of stearic acid with anE-caprolactone/tetraethylene pentamine adduct: ##STR8##

In an alternative embodiment, the reaction between the lactone-polyoladduct and the acylating agent may be exemplified by the followingreaction scheme which represents the esterification of the dimer acid ofisostearic acid with an E-caprolactone/pentaerythritol adduct: ##STR9##

In still another alternative a lactone/amino alcohol adduct is reactedwith the carboxylic acylating agent to form a oxazoline type dispersant.

The preparation of the oxazoline type dispersants of this invention canbe illustrated by the reactions between isostearic acid andE-caprolactone/THAM adducts as follows: ##STR10##

Further aspects of the present invention reside in the formation ofmetal complexes and other post-treatment derivatives, e.g., boratedderivatives, of the novel additives prepared in accordance with thisinvention. Suitable metal complexes may be formed in accordance withknown techniques of employing a reactive metal ion species during orafter the formation of the present C₅ -C₉ lactone derived dispersantmaterials. Complex-forming metal reactants include the nitrates,thiocyanates, halides, carboxylates, phosphates, thio-phosphates,sulfates, and borates of transition metals such as iron, cobalt, nickel,copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium,platinum, cadmium, lead, silver, mercury, antimony and the like. Priorart disclosures of these complexing reactions may be found in U.S. Pat.No. 3,306,908 and U.S. Pat. No. Re. 26,433.

Post-treatment compositions include those formed by reacting the noveladditives of the present invention with one or more post-treatingreagents, usually selected from the group consisting of boron oxide,boron oxide hydrate, boron halides, boron acids, sulfur, sulfurchlorides, phosphorous sulfides and oxides, carboxylic acid or anhydrideacylating agents, epoxides and episulfides and acrylonitriles. Thereaction of such post-treating agents with the novel additives of thisinvention is carried out using procedures known in the art. For example,boration may be accomplished in accordance with the teachings of U.S.Pat. No. 3,254,025 by treating the C₅ -C₉ lactone derived additivecompound with a boron oxide, halide, ester or acid. Treatment may becarried out by adding about 1-3 wt. % of the boron compound, preferablyboric acid, and heating and stirring the reaction mixture at about 135°C. to 165° C. for 1 to 5 hours followed by nitrogen stripping andfiltration, if desired. Mineral oil or inert organic solvents facilitatethe process.

The Compositions

The lactone derived additives of the present invention have been foundto prossess very good dispersant properties as measured herein in a widevariety of environments.

Accordingly, the lactone derived adducts are used by incorporation anddissolution into an oleaginous material such as fuels and lubricatingoils.

When the dispersants of this invention are used in normally liquidpetroleum fuels such as middle distillates boiling from about 150° to800° F., including kerosene, diesel fuels, home heating fuel oil, jetfuels, etc., a concentration of the additive in the fuel in the range oftypically from about 0.001 to about 0.5, and preferably 0.001 to about0.1 weight percent, based on the total weight of the composition, willusually be employed.

The lactone derived dispersants find their primary utility inlubricating oil compositions which employ a base oil in which theadditives are dissolved or dispersed.

Such base oils may be natural or synthetic although the natural baseoils will derive a greater benefit.

Thus, base oils suitable for use in preparing lubricating compositionsof the present invention include those conventionally employed ascrankcase lubricating oils for spark-ignited and compression-ignitedinternal combustion engines, such as automobile and truck engines,marine and railroad diesel engines, and the like. Advantageous resultsare also achieved by employing the dispersant additives of the presentinvention in base oils conventionally employed in and/or adapted for useas power transmitting fluids such as automatic transmission fluids,tractor fluids, universal tractor fluids and hydraulic fluids, heavyduty hydraulic fluids, power steering fluids and the like. Gearlubricants, industrial oils, pump oils and other lubricating oilcompositions can also benefit from the incorporation therein of theadditives of the present invention.

Thus, the additives of the present invention may be suitablyincorporated into synthetic base oils such as alkyl esters ofdicarboxylic acids, polyglycols and alcohols, polyalphaolefins, alkylbenzenes, organic esters of phosphoric acids, polysilicone oils, etc.

Natural base oils include mineral lubricating oils which may vary widelyas to their crude source, e.g., whether paraffinic, naphthenic, mixed,paraffinic-naphthenic, and the like; as well as to their formation,e.g., distillation range, straight run or cracked, hydrofined, solventextracted and the like.

More specifically, the natural lubricating oil base stocks which can beused in the compositions of this invention may be straight minerallubricating oil or distillates derived from paraffinic, naphthenic,asphaltic, or mixed base crudes, or, if desired, various blends oils maybe employed as well as residuals, particularly those from whichasphaltic constituents have been removed. The oils may be refined byconventional methods using acid, alkali, and/or clay or other agentssuch as aluminum chloride, or they may be extracted oils produced, forexample, by solvent extraction with solvents of the type of phenol,sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene,crotonaldehyde, etc.

The lubricating oil base stock conveniently has a viscosity of typicallyabout 2.5 to about 12, and preferably about 2.5 to about 9 cs. at 100°C.

Thus, the lactone derived additives of the present invention can beemployed in a lubricating oil composition which comprises lubricatingoil, typically in a major amount, and the dispersant additive, typicallyin a minor amount, which is effective to impart enhanced dispersancy,relative to the absence of the additive. Additional conventionaladditives selected to meet the particular requirements of a selectedtype of lubricating oil composition can be included as desired.

The dispersants of this invention are oil-soluble, dissolvable in oilwith the aid of a suitable solvent, or are stably dispersible materials.Oil-soluble, dissolvable, or stably dispersible as that terminology isused herein does not necessarily indicate that the materials aresoluble, dissolvable, miscible, or capable of being suspended in oil inall proportions. It does mean, however, that the dispersant additives,for instance, are soluble or stably dispersible in oil to an extentsufficient to exert their intended effect in the environment in whichthe oil is employed. Moreover, the additional incorporation of otheradditives may also permit incorporation of higher levels of a particulardispersant, if desired.

Accordingly, while any effective amount of the dispersant additives canbe incorporated into the lubricating oil composition, it is contemplatedthat such effective amount be sufficient to provide said lube oilcomposition with an amount of the additive of typically from about 0.01to about 15 e.g., 0.1 to 10, and preferably from about 0.1 to about 7wt. %, based on the weight of said composition.

The dispersant additives of the present invention can be incorporatedinto the lubricating oil in any convenient way. Thus, they can be addeddirectly to the oil by dispersing, or dissolving the same in the oil atthe desired level of concentration typically with the aid of a suitablesolvent such as toluene, or tetrahydrofuran. Such blending can occur atroom temperature or elevated temperatures. Alternatively, the dispersantadditives may be blended with a suitable oil-soluble solvent and baseoil to form a concentrate, and then blending the concentrate withlubricating oil base stock to obtain the final formulation. Concentrateswill typically contain from about 20 to about 80 wt. %, preferably fromabout 20 to about 60 wt. %, by weight dispersant additive, and typicallyfrom about 80 to about 20%, preferably from about 60 to about 20% byweight base oil, based on the concentrate weight.

The lubricating oil base stock for the dispersant additives of thepresent invention typically is adapted to perform a selected function bythe incorporation of additives therein to form lubricating oilcompositions (i.e., formulations).

Representative additives typically present in such formulations includeviscosity modifiers, corrosion inhibitors, oxidation inhibitors,friction modifiers, other dispersants, anti-foaming agents, anti-wearagents, pour point depressants, detergents, rust inhibitors and thelike.

Viscosity modifiers impart high and low temperature operability to thelubricating oil and permit it to remain shear stable at elevatedtemperatures and also exhibit acceptable viscosity or fluidity at lowtemperatures.

Viscosity modifiers are generally high molecular weight hydrocarbonpolymers including polyesters. The viscosity modifiers may also bederivatized to include other properties or functions, such as theaddition of dispersancy properties.

These oil soluble viscosity modifying polymers will generally havenumber average molecular weights of from 10³ to 10⁶, preferably 10⁴ to10⁶, e.g., 20,000 to 250,000, as determined by gel permeationchromatography or membrane osmometry.

Representative examples of suitable viscosity modifiers are any of thetypes known to the art including polyisobutylene, copolymers of ethyleneand propylene, polymethacrylates, methacrylate copolymers, copolymers ofan unsaturated dicarboxylic acid and vinyl compound, interpolymers ofstyrene and acrylic esters, and styrene/isoprene copolymers.

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are phosphosulfurizedhydrocarbons and the products obtained by reaction of aphosphosulfurized hydrocarbon with an alkaline earth metal oxide orhydroxide, preferably in the presence of an alkylated phenol or of analkylphenol thioester, and also preferably in the presence of carbondioxide. Phosphosulfurized hydrocarbons are prepared by reacting asuitable hydrocarbon such as a terpene, a heavy petroleum fraction of aC₂ to C₆ olefin polymer such as polyisobutylene, with from 5 to 30 wt. %of a sulfide of phosphorus for 1/2 to 15 hours, at a temperature in therange of 150° to 600° F. Neutralization of the phosphosulfurizedhydrocarbon may be effected in the manner taught in U.S. Pat. No.1,969,324.

Oxidation inhibitors reduce the tendency of mineral oils to deterioratein service which deterioration can be evidenced by the products ofoxidation such as sludge and varnish-like deposits on the metal surfacesand by viscosity growth. Such oxidation inhibitors include alkalineearth metal salts of alkylphenolthioesters having preferably C₅ to C₁₂alkyl side chains, e.g., calcium nonylphenol sulfide, bariumt-octylphenyl sulfide, dioctylphenylamine, phenylalphanaphthylamine,phosphosulfurized or sulfurized hydrocarbons, etc.

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable modifiers are found in U.S. Pat. No.3,933,659 which discloses fatty acid esters and amides; U.S. Pat. No.4,176,074 which describes molybdenum complexes of polyisobutyenylsuccinic anhydride-amino alkanols; U.S. Pat. No. 4,105,571 whichdiscloses glycerol esters of dimerized fatty acids; U.S. Pat. No.3,779,928 which discloses alkane phosphonic acid salts; U.S. Pat. No.3,778,375 which discloses reaction products of a phosphonate with anoleamide; U.S. Pat. No. 3,852,205 which discloses S-carboxyalkylenehydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl succinamic acidand mixtures thereof; U.S. Pat. No. 3,879,306 which disclosesN-(hydroxyalkyl)alkenyl-succinamic acids or succinimides; U.S. Pat. No.3,932,290 which discloses reaction products of di-(lower alkyl)phosphites and epoxides; and U.S. Pat. No. 4,028,258 which discloses thealkylene oxide adduct of phosphosulfurized N-(hydroxyalkyl) alkenylsuccinimides. The disclosures of the above references are hereinincorporated by reference. The most preferred friction modifiers aresuccinate esters, or metal salts thereof, of hydrocarbyl substitutedsuccinic acids or anhydrides and thiobis alkanols such as described inU.S. Pat. No. 4,344,853.

Dispersants maintain oil insolubles, resulting from oxidation duringuse, in suspension in the fluid thus preventing sludge flocculation andprecipitation or deposition on metal parts. Suitable dispersants includehigh molecular weight alkyl succinates, the reaction product ofoil-soluble polyisobutylene succinic anhydride with ethylene amines suchas tetraethylene pentamine and borated salts thereof.

Pour point depressants lower the temperature at which the fluid willflow or can be poured. Such depressants are well known. Typically ofthose additives which usefully optimize the low temperature fluidity ofthe fluid are C₈ -C₁₈ dialkylfumarate vinyl acetate copolymers,polymethacrylates, and wax naphthalene. Foam control can be provided byan antifoamant of the polysiloxane type, e.g., silicone oil andpolydimethyl siloxane.

Anti-wear agents, as their name implies, reduce wear of metal parts.Representatives of conventional anti-wear agents are zincdialkyldithiophosphate, and zinc diaryldithiosphate.

Detergents and metal rust inhibitors include the metal salts ofsulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkylsalicylates, naphthenates and other oil soluble mono- and di-carboxylicacids. Highly basic (viz, overbased) metal salts, such as highly basicalkaline earth metal sulfonates (especially Ca and Mg salts) arefrequently used as detergents. Representative examples of suchmaterials, and their methods of preparation, are found in co-pendingSer. No. 754,001, filed July 11, 1985, the disclosure of which is herebyincorporated by reference.

Some of these numerous additives can provide a multiplicity of effects,e.g., a dispersant-oxidation inhibitor. This approach is well known andneed not be further elaborated herein.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts which are effective to providetheir normal attendant function. Representative effective amounts ofsuch additives are illustrated as follows:

    ______________________________________                                        Additive           Vol %    Wt % a.i.                                         ______________________________________                                        Viscosity Modifier  .01-4   .01-4                                             Corrosion Inhibitor                                                                              0.01-1   .01-1.5                                           Oxidation inhibitor                                                                              0.01-1   .01-1.5                                           Dispersant          0.1-7   0.1-8                                             Pour Point Depressant                                                                            0.01-1   .01-1.5                                           Anti-Foaming Agents                                                                               0.001-0.1                                                                             .001-0.15                                         Anti-Wear Agents   0.001-1  .001-1.5                                          Friction Modifiers 0.01-1   .01-1.5                                           Detergents/Rust Inhibitors                                                                         .01-2.5                                                                              .01-3                                             Mineral Oil Base   Balance  Balance                                           ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the dispersant (in concentrate amountshereinabove described), together with one or more of said otheradditives (said concentrate when constituting an additive mixture beingreferred to herein as an additive-package) whereby several additives canbe added simultaneously to the base oil to form the lubricating oilcomposition. Dissolution of the additive concentrate into thelubricating oil may be facilitated by solvents and by mixing accompaniedwith mild heating, but this is not essential. The concentrate oradditive-package will typically be formulated to contain the dispersantadditive and optional additional additives in proper amounts to providethe desired concentration in the final formulation when theadditive-package is combined with a predetermined amount of baselubricant. Thus, the dispersant of the present invention can be added tosmall amounts of base oil or other compatible solvents along with otherdesirable additives to form additive-packages containing activeingredients in collective amounts of typically from about 2.5 to about90%, and preferably from about 5 to about 75%, and most preferably fromabout 8 to about 50% by weight additives in the appropriate proportionswith the remainder being base oil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein are based on activeingredient (a.i.) content of the additive, and/or upon the total weightof any additive-package, or formulation which will be the sum of thea.i. weight of each additive plus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all parts are parts by weight and all molecularweights are number average molecular weights, unless otherwise noted andwhich include preferred embodiments of the invention.

EXAMPLE 1 Preparation of Isostearic Acid/E-Caprolactone-TEPA Dispersant

About 37.8 g (0.2 mole) of tetraethylene pentamine (TEPA) were mixedwith 22.8 g (0.2 mole) of E-caprolactone (CL) in a 500 ml flask. Themixture stirred at room temperature for two hours and then heated slowlyto 110° C. The mixture was kept at that temperature for one hour whilestirring under a nitrogen blanket.

Thereafter, 176.4 g of isostearic acid (ISA) were added over a period of40 minutes while maintaining the temperature at 110° C. The reactiontemperature was raised to 160° C. over a period of three hours. A vacuumwas then applied and the reaction mixture was heated to 190° C. for twohours.

EXAMPLE 2 Simultaneous Reaction of TEPA E-Caprolactone and IsostearicAcid

About 176.4 g (0.62 moles) of isostearic acid 22.8 g (0.2 mole) ofE-caprolactone and 37.8 g (0.2 moles) of TEPA were added to a reactionsflask. The reaction mixture was blanketed with nitrogen and heated to160° C. for two hours. A vacuum was applied and the reaction mass washeated to 190° C. for two hours.

EXAMPLE 3 Preparation of Isostearic Acid-TEPA Reaction Product

About 88.2 g (0.31 moles) of isostearic acid were added to a reactionflask and 37.8 g (0.2 moles) TEPA were added over a 30 minute period.Then another 88.2 g of isostearic acid were added over a 30 minuteperiod. The reaction temperature was raised to 160° C. over a three hourperiod. The nitrogen blanket was removed, a vacuum was applied, and thetemperature was raised to 190° C. for two hours.

Samples of the various reaction products of Examples 1, 2 and 3, alongwith samples of several commercially employed dispersants were thensubjected to a standard sludge inhibition bench test (SIB) and astandard varnish inhibition bench test (VIB).

The SIB and VIB tests forecast the performance of a lubricant in agasoline engine. These tests are described below. The SIB test employs aused crankcase mineral lubricating oil composition having an originalviscosity of about 325 SUS at 37.8° C. that have been used in a taxicabthat was driven generally for short trips only, thereby causing abuildup of a high concentration of sludge precursors. The oil usedcontains only a refined base mineral oil, a viscosity index improver, apour point depressant and zinc dialkyl-dithiophosphate antiwearadditives. The oil contains no sludge dispersants. Such oil is acquiredby draining and refilling the taxicab crankcases at about 1000-2000 mileintervals.

The SIB test is conducted in the following manner: The used crankcaseoil is freed of sludge by centrifuging for one half hour at about 39.000gravities (gs). The resulting clear bright red oil is then decanted fromthe insoluble particles. However, the supernatant oil still containsoil-soluble sludge precursors which, under the conditions employed bythis test, tend to form additional oil-insoluble deposits of sludge. Thesludge inhibiting properties of the additives being tested aredetermined by adding to portions of the used oil 0.5 wt. % on an activebasis, of the particular additive being tested. Ten grams of each samplebeing tested is placed in a stainless steel centrifuge tube and isheated at 140° C. for 16 hours in the presence of air. Following theheating, the tube containing the oil being tested is cooled and thencentrifuged for 30 minutes at about 39,000 gs. Any deposits of newsludge that form in this step are separated from the decantingsupernatant oil and then carefully washed with 15 ml. of pentane toremove all remaining oils from the sludge. The weight, in milligrams, ofthe new solid sludge that forms in the test is determined by drying theresidue and weighing it. The results are reported as milligrams ofsludge per ten grams of oil thus measuring differences as small as onepart per ten thousand. The less new sludge formed, the more effective isthe additive as a dispersant. In other words, if the additive iseffective, it will hold at least a portion of the new sludge that formson heating and oxidation, stably suspended in the oil so that it doesnot precipitate during the centrifuging period.

In the VIB test, a test sample consisting of ten grams of lubricatingoil containing 0.5 wt. %, on an active basis, of the additive beingevaluated is used. The test oil is a commercial lubricating oil obtainedfrom a taxi after about 2000 miles of driving with said lubricating oil.Each sample is heat soaked overnight at about 140° C. and thereaftercentrifuged to remove the sludge. The supernatant fluid of each sampleis subjected to heat cycling from about 150° C. to room temperature overa period of 3.5 hours at a frequency of about two cycles per minute.During the heating phase, a gas containing a mixture of 0.7 volumepercent SO₂, 1.4 volume percent NO and the balance air is bubbledthrough the test samples and during the cooling phase, water vapor wasbubbled through the test samples. At the end of the test period, whichtesting cycle can be repeated as necessary to determine the inhibitingeffect of any additive, the wall surfaces of the test flasks in whichthe samples were contained are visually evaluated as to the varnishinhibition. The amount of varnish deposited on the walls is rated atvalues of from one to eleven with the higher number being the greateramount of varnish. It has been found that this test forecasts thevarnish results obtained as a consequence of carrying out the ASTM MS-VDengine tests which is described more fully hereinbelow.

Table I, which follows, summarizes the compositions tested and the testresults:

                                      TABLE I                                     __________________________________________________________________________                  TEPA.sup.1                                                                        CL.sup.2                                                                          ISA.sup.3                                                                         Viscosity,                                          Example                                                                              Process                                                                              (moles)                                                                           (moles)                                                                           (moles)                                                                           100° C., CS                                                                  SIB.sup.4                                                                         SIB.sup.5                                 __________________________________________________________________________    1      Pre-reacted.sup.6                                                                    1   2   3.1 112.4 7.91                                                                              3                                                TEPA-CL                                                                2      Simultaneous.sup.7                                                                   1   1   3.1  90.4 6.93                                                                               33/4                                     3      Simultaneous.sup.8                                                                   1   0   3.1  58.6 1.35                                                                              4                                                Addition                                                               PIBSA 1.sup.9                   3.26                                                                              7                                         PIBSA 2.sup.10                  2.23                                                                              5                                         ISA TEPA.sup.11           105.2  .93                                                                               41/4                                     __________________________________________________________________________     .sup.1 tetraethylene pentamine                                                .sup.2 caprolactone                                                           .sup.3 isostearic acid                                                        .sup.4 sludge inhibition bench test rating in milligrams sludge per 10        milligrams oil                                                                .sup.5 varnish inhibition bench test rating on basic of 1 to 11; the          higher the rating, the greater the amount of varnish deposited                .sup.6 TEPA reacted with CL to form adduct which is then reacted with ISA     .sup.7 simultaneous reaction of TEPA, CL and ISA                              .sup.8 simultaneous reaction of TEPA and ISA                                  .sup.9 polyisobutenyl succinic anhydridge dispersant; number average Mw o     polyisobutylene moieties (PIB) = 940; ratio of succinic anhydride (SA)        moieties to PIB moieties = 1.04                                               .sup.10 polyisobutenyl succinic anhydridge dispersant; number average Mw      of polyisobutylene moieties (PIB) = 1300; ratio of succinic anhydride (SA     moieties to PIB moieties = 1.31                                               .sup.11 pilot plant version of Example 3.                                

The data in Table I indicate that the dispersants prepared by reactingisostearic acid with the caprolactone-TEPA adduct (Example 1) showed animproved VIB value when compared to the dispserants prepared by thesimultaneous addition of TEPA, CL and ISA (Example 2) or thesimultaneous addition of TEPA and ISA, without any addition of CL(Example 3). The data also indicate that the dispersant prepared inaccordance with the invention exhibits substantially better VIB ratingsthan commercially employed dispersants based on polyisobutenyl succinicanhydride (PIBSA 1 and PIBSA 2) and (ISA TEPA), and that while there isan increase in viscosity with then CL is present in the dispersants, theoverall viscosity of the pre-reacted TEPA-CL/ISA dispersant iscomparable to that of the ISA TEPA dispersant. It will be noted that theSIB and VIB tests of the products shown in Table 1 were based on a 100%active ingredient material so that a relative comparison to the ISA TEPAdispersant could be made. It will be noted also that although the SIBvalues are somewhat higher for the dispersants which contain CL, all ofthe SIB values shown in Table 1 are well within commercially acceptablelimits.

Other lactone adduct dispersants in accordance with the presentinvention are illustrated in Examples 4-9, which follow.

EXAMPLE 4 Preparation of E-Caprolactone-THAM Adduct

About 121.0 g (1.0 mole) of 2-amino-2-(hydroxymethyl)-1,3-propanediol(THAM) was combined with 114.0 g (1.0 mole) of E-Caprolactone and 0.1 gstannous octanoate Sn(OCT)₂. As the reaction mixture was slowly heatedto 150° C., a clear solution was obtained. Infrared analysis of thereaction product showed no unreacted caprolactone. Upon heating theproduct cyclized to a hydroxy-oxazoline, and a strong absorption band at6.0 microns in the infrared spectrum was observed. The product analyzedfor 50.94% C, 9.29% H and 5.79% N.

EXAMPLE 5 Preparation of Dimer Acid/E-Caprolactone-THAM AdductDispersant

About 141.2 g (0.25 moles) of a dimer of linoleic acid (Empol 1010 fromEmery Chemical Company), and 117.5 g (0.5 moles) of thecaprolactone-THAM adduct of Example 4 were charged into a reactionflask, along with 0.1 g of para-toluene sulfonic acid (p-TOSH). Thereaction mixture was slowly heated to 180° C. while stirring under anitrogen blanket. At the end of four hours at 180° C., an infraredanalysis of the reaction mixture showed complete conversion to thedesired ester oxazoline. The reaction mixture as then cooled andcollected.

EXAMPLE 6 Preparation of Octadecenyl SuccinicAnhydride/E-Caprolactone-THAM Adduct Dispersant

About 87.5 g (0.25 moles) of octadecenyl succinic anhydride (OSA), 117.4g (0.5 moles) of the CL-THAM adduct of Example 4 and 0.1 g of p-TOSHwere added to a 500 ml. flask and slowly heated to 180° C. while under anitrogen atmosphere. The reaction mixture was checked periodically byinfrared analysis. At the end of the fourth hour at 180° C., while undernitrogen, the infrared analysis showed complete conversion to thedesired ester oxazoline. The reaction mixture was then cooled andcollected.

EXAMPLE 7 Preparation of Isostearic Acid/E-Caprolactone-THAM AdductDispersant

About 28.1 g (0.1 mole) of isostearic acid and 23.5 g (0.1 mol) of theCL-THAM adduct of Example 4 were added to a reaction flask and heated to180° C. to distill off the water of reaction. The reaction mixture washeated at 180° C. for four hours with mild nitrogen sparging. Aninfrared analysis of the product showed the desired ester oxazoline. Theresidue was diluted in solvent 150 neutral mineral oil to make a 50%active ingredient solution and was collected.

EXAMPLE 8 Preparation of E-Caprolactone Pentaerythritol Adduct

About 163.2 g (1.2 moles) of pentaerythritol (PE) and 136.2 g (1.2moles) of E-caprolactone were mixed with 0.1 g of Sn(OCT)₂ and heatedslowly to 150° C. for one hour. An infrared analysis of the productshowed complete reaction of the caprolactone and PE. The product waspoured into a large excess of methanol and no unreacted PE precipitatedout of the solution. The methanol was stripped off and the residue wascollected. The product became a waxy solid upon standing at roomtemperature.

Example 9 Preparation of Dimer Acid E-Caprolactone-PE Adduct Dispersant

About 141.2 g (0.25 moles) of Empol 1010 dimer acid from Emery ChemicalCompany, about 137.5 g (approximately 0.5 moles) of the caprolactone-PEadduct of Example 8, and about 0.1 g of p-TOSH were added to a 500 mlflask and slowly heated to 180° C. while stirring under a nitrogenatmosphere. At the end of four hours at 180° C., an infrared analysis ofthe reaction mixture showed complete conversion to the desired ester.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in light of the foregoingdisclosure and illustrative examples, tables and discussion, withoutdeparting from the spirit and scope of the disclosure or from the scopeof the invention as set forth in the following claims.

What is claimed is:
 1. A C₅ -C₉ lactone adduct material useful as alubricating oil additive formed by reacting an aliphatic hydrocarbylsaturated or unsaturated, natural or synthetic, straight chain orbranched chain monocarboxylic or dicarboxylic acylating agent havingfrom about 12 to about 165 total carbon atoms with the reaction productof a C₅ -C₉ lactone with an aliphatic polyhydric alcohol containing upto about 100 carbon atoms and from about 2 to about 10 hydroxyl groups,said aliphatic acylating agent having at least about twelve carbon atomsin said straight or branched chain to produce lactone adduct materialthat is hydrocarbon soluble.
 2. The C₅ -C₉ lactone adduct material ofclaim 1, wherein said acylating agent is a member selected from thegroup of long chain fatty acids or dimers thereof and hydrocarbylsubstituted C₄ -C₁₀ monounsaturated dicarboxylic acid materials, whereinsaid hydrocarbyl group contains from about twelve to about eighteencarbon atoms.
 3. The C₅ -C₉ lactone adduct material of claim 2, whereinsaid lactone is E-caprolactone.
 4. The C₅ -C₉ lactone adduct material ofclaim 3, wherein said acylating agent is selected from the groupconsisting of isostearic acid, stearic acid, linoleic acid, oleic acid,dimers of said acids and octadecenyl succinic anhydride.
 5. The C₅ -C₉lactone adduct material of claim 1, wherein said polyhdric alcohol is analiphatic alcohol containing from 3 to 15 carbon atoms and at leastthree hydroxyl groups.
 6. The C₅ -C₉ lactone adduct material of claim 5,wherein said polyhydric alcohol is a member selected from the groupconsisting of glycerol, erythritol, pentaerythritol, mannitol, sorbitol,1,2,4-hexanetriol and tetrahydroxy pentane.
 7. The C₅ -C₉ lactone adductmaterial of claim 4, wherein said polyhydric alcohol is an aliphaticalcohol containing from 3 to 15 carbon atoms and at least three hydroxylgroups.
 8. The C₅ -C₉ lactone adduct material of claim 7, wherein saidpolyhydric alcohol is a member selected from the group consisting ofglycerol, erythritol, pentaerythritol, mannitol, sorbitol,1,2,4-hexanetriol and tetrahydroxy pentane.
 9. The C₅ -C₉ lactone adductmaterial of claim 1, which has been post-treated with a borating agentselected from the group consisting of boron oxide, boron oxide hydrate,boron halides, boron esters and boron acids.
 10. A process for preparinga C₅ -C₉ lactone adduct material useful as a lubricating oil additive,which comprises the steps of:i) reacting a C₅ -C₉ lactone with analiphatic polyhydric alcohol having up to 100 carbon atoms and fromabout 2 to about 10 hydroxyl groups to form a lactone adductintermediate product; and ii) reacting said intermediate product with analiphatic hydrocarbyl saturated or unsaturated, natural or synthetic,straight chain or branched chain monocarboxylic or dicarboxylicacylating agent having from about twelve to about eighteen total carbonatoms and at least twelve carbon atoms in the hydrocarbyl group.
 11. Theprocess of claim 10, wherein said lactone is E-caprolactone.
 12. Theprocess of claim 11, wherein said acylating agent is selected from thegroup consisting of isostearic acid, stearic acid, linoleic acid, oleicacid, dimers of said acids and octadecenyl succinic anhydride.
 13. Theprocess of claim 10, wherein said polyhdric alcohol is an aliphaticalcohol containing from 3 to 15 carbon atoms and at least three hydroxylgroups.
 14. The process of claim 13, wherein said polyhydric alcohol isa member selected from the group consisting of glycerol, erythritol,pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxypentane.
 15. The process of claim 10, further comprising the step ofpost-treating the C₅ -C₉ lactone adduct material with a borating agentselected from the group consisting of boron oxide, boron oxide hydrate,boron halides, boron esters and boron acids.
 16. An oleaginouscomposition comprising (I) an oleaginous material selected from thegroup consisting of lubricating oils and (II) a C₅ -C₉ lactone adductmaterial, said adduct material being prepared by reacting (i) a C₅ -C₉lactone with (ii) an aliphatic polyhydric alcohol containing up to about100 total carbon atoms and from about 2 to about 100 total carbon tomsand from about 2 to about 10 hydroxyl groups to form an intermediatelactone adduct, and then reacting said intermediate lactone adduct with(iii) an aliphatic hydrocarbyl saturated or unsaturated, natural orsynthetic, straight chain or branched chain monocarboxylic ordicarboxylic acylating agent having from about 12 to 165 total carbonatoms and at least about twelve carbon atoms in said straight orbranched chain to insure that the resulting lactone adduct material ishydrocarbon soluble.
 17. The oleaginous composition of claim 16, whereinsaid acylating agent is a member selected from the group of long chainfatty acids or dimers thereof and hydrocarbyl substituted C₄ -C₁₀monounsaturated dicarboxylic acid materials, wherein said hydrocarbylgroup contains from about twelve to about eighteen carbon atoms.
 18. Theoleaginous composition of claim 17, wherein said lactone isE-caprolactone.
 19. The oleaginous composition of claim 18, wherein saidacylating agent is selected from the group consisting of isostearicacid, stearic acid, linoleic acid, oleic acid, dimers of said acids andoctadecenyl succinic anhydride.
 20. The oleaginous composition of claim16, wherein said polyhdric alcohol is an aliphatic alcohol containingfrom 3 to 15 carbon atoms and at least three hydroxyl groups.
 21. Theoleaginous composition of claim 20, wherein said polyhydric alcohol is amember selected from the group consisting of glycerol, erythritol,pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxypentane.
 22. The oleaginous composition of claim 16, wherein said C₅ -C₉lactone adduct material has been post-treated with a borating agentslected from the group consisting of boron oxide, boron oxide hydrate,boron halides, boron esters and boron acids.
 23. A lubricating oilcomposition comprising lubricating oil and about 0.01 to 15 wt. % of theC₅ -C₉ lactone adduct material of claim
 3. 24. A lubricating oilcomprising a major amount of lubricating oil and about 0.1 to 10 wt. %of the C₅ -C₉ lactone adduct material of claim
 3. 25. A lubricating oilcomprising a major amount of lubricating oil and about 0.01 to 15 wt. %of the C₅ -C₉ lactone adduct material of claim
 4. 26. A lubricating oilcomprising a major amount of lubricating oil about 0.1 to 10 wt. % ofthe C₅ -C₉ lactone adduct material of claim
 5. 27. A lubricating oilcomprising a major amount of lubricating oil about 0.1 to 10 wt. % ofthe C₅ -C₉ lactone adduct material of claim
 9. 28. A lubricating oilsoluble dispersant useful as an oil additive, comprising the product ofa reaction mixture comprising:(i) an aliphatic hydrocarbyl saturated orunsaturated natural or synthetic, straight chain or branched chainmonocarboxylic or dicarboxylic acylating agent having from about 12 toabout 165 total carbon atoms; and (ii) a C₅ -C₉ lactone adduct formed byreacting (a) a C₅ -C₉ lactone with (b) an aliphatic polyhydric alcoholcontaining up to about 100 total carbon atoms and from about 2 to about10 hydroxyl groups,wherein there are from 1 to about 10 C₅ -C₉ lactonederived moieties per unit of said adduct (II) used in the reaction. 29.An oil soluble dispersant according to claim 28, wherein said C₅ -C₉lactone is caprolactone.
 30. An oil soluble dispersant according toclaim 28, wherein said polyhydric alcohol is an aliphatic alcoholcontaining from 3 to 15 carbon atoms and at least three hydroxyl groups.31. An oil soluble dispersant according to claim 30, wherein saidpolyhydric alcohol is a member selected from the group consisting ofglycerol, erythritol, pentaerythritol, mannitol, sorbitol,1,2,4-hexanetriol and tetrahydroxy pentane.
 32. An oil solubledispersant according to claim 29, which has been post-treated with aborating agent selected from the group consisting of boron oxide, boronoxide hydrate, boron halides, boron esters and boron acids.
 33. Alubricating oil soluble reaction product useful as an oil additiveof:(a) an aliphatic hydrocarbyl saturated or unsaturated, natural orsynthetic, straight chain or branched chain monocarboxylic ordicarboxylic acylating agent having from about 12 to about 18 totalcarbon atoms (b) aliphatic polyhydric alcohol containing up to about 100total carbon atoms and from 2 to about 10 hydroxyl groups, and (c) C₅-C₉ lactone,wherein (b) is first reacted with (c) and the resultingproduct is then reacted with (a), and wherein there are about 0.5 to 20molar proportions of (c) per molar proportion of said reaction product.34. An oil soluble reaction product according to claim 33 whereinwherein (c) is E-caprolactone, and wherein there are about 1 to 5 molarproportions of (c) per molar proportion of said reaction product.
 35. Alubricating oil composition comprising lubricating oil and an oilsoluble reaction product useful as an oil additive, said reactionproduct being the product of reaction of the intermediate product formedby reacting (a) a C₅ -C₉ lactone with an aliphatic polyhydric alcoholcontaining up to about 100 total carbon atoms and from about 2 to about10 hydroxyl groups, wherein there are 0.2 to 100 molar proportions of(b) in said intermediate product, further reacted with (c) an aliphatichydrocarbyl saturated or unsaturated, natural or synthetic, straightchain or branched chain monocarboxylic or dicarboxylic acylating agenthaving from about 12 to about 18 total carbon atoms.
 36. A lubricatingoil composition according to claim 35, wherein (a) is caprolactone, andwherein there are from about one to about five molar proportions ofcaprolactone per molar proportion of product obtained by the reaction of(a) with (b).
 37. A lubricating crankcase motor oil composition forautomotive vehicles and trucks comprising a major amount of lubricatingoil; from about 0.01 to 15 wt. % of a dispersant formed by reacting analiphatic hydrocarbyl saturated or unsaturated, natural or synthetic,straight chain or branched chain monocarboxylic or dicarboxylicacylating agent having from about 12 to about 18 total carbon atoms withthe reaction product of a C₅ -C₉ lactone and an aliphatic polyhydricalcohol containing up to about 100 total carbon atoms and from about 2to about 10 hydroxyl groups, wherein said dispersant has about one tofive molar proportion of acylating agent moieties; and about 3 to 25 wt.% of a metal containing detergent additive.
 38. A composition accordingto claim 37, wherein said C₅ -C₉ lactone is caprolactone.
 39. Acomposition according to claim 38, wherein said composition alsocontains an effective amount of a zinc dihydrocarbyl dithiophosphate.40. A composition according to claim 39 wherein said dispersant has beenpost-treated with a borating agent slected from the group consisting ofboron oxide, boron oxide hydrate, boron halides, boron esters and boronacids.
 41. An additive concentrate comprising about 20 to 80 wt. %lubricating oil and 20 to 80 wt. % of a dispersant which is a C₅ -C₉lactone adduct material formed by first reacting about 0.2 to 100 molarproportions of a C₅ -C₉ lactone per molar proportion of an aliphaticpolyhydric alcohol containing up to about 100 total carbon atoms andfrom about 2 to about 10 hydroxyl groups to form a lactone adductintermediate, and then reacting said intermediate with an aliphatichydrocarbyl saturated or unsaturated, natural or synthetic, straightchain or branched chain monocarboxylic or dicarboxylic acylating agenthaving from about 12 to about 18 total carbon atoms.
 42. A concentrateaccording to claim 41, wherein said C₅ -C₉ lactone is caprolactone andwhich also contains an effective amount of a viscosity modifier.
 43. Aconcentrate according to claim 42, which also contains an effectiveamount of a zinc dihydrocarbyl dithiophosphate.
 44. A concentrateaccording to claim 41, wherein said C₅ -C₉ lactone adduct material hasbeen post-treated with a borating agent selected from the groupconsisting of boron oxide, boron oxide hydrate, boron halides, boronesters and boron acids.
 45. An additive concentrate comprising about 20to 80 wt. % lubricating oil and about 20 to 80 wt. % of an oil solublereaction product of a caprolactone adduct and an acylating agentselected from the group consisting of long chain fatty acids, long chainfatty acid dimers and hydrocarbyl substituted C₄ to C₁₀ monounsaturateddicarboxylic acid producing material having from about twelve to about18 carbon atoms in said hydrocarbyl substituent, said caprolactoneadduct being prepared by reacting caprolactone with an aliphaticpolyhydric alcohol containing up to about 100 total carbon atoms andfrom about 2 to about 10 hydroxyl groups.
 46. An additive concentrateaccording to claim 45, wherein said hydrocarbyl substituted C₄ to C₁₀acid producing material is octadecenyl succinic anhydride.
 47. Anadditive concentrate according to claim 45, wherein said long chainfatty acids and said long chain fatty acid dimers are selected from thegroup consisting of isostearic acid, stearic acid, linoleic acid, oleicacid and dimers thereof.